Unveiling the correlation between the catalytic efficiency and acidity of a metal-free catalyst in a hydrogenation reaction. A theoretical case study of the hydrogenation of ethene catalyzed by a superacid arising from a superhalogen.

A systematic quantum-chemical study of the hydrogenation of ethene, catalyzed by strong acids HX (X = F, Cl, Br) and superacids HA (A = MgX 3 , Mg 2 X 5 ; X = F, Cl, Br) arising from octet superhalogens is explored. Two possible paths are proposed, concerted and stepwise, and the calculated results show that the concerted path is more favorable than the stepwise path. Compared to the hydrogenation reaction without any catalyst, the improvement of the catalytic efficiency of the superacid HA (A = MgX 3 , Mg 2 X 5 ) is high, up to 38.8 to 59.4%. Compared to the strong acid HX (X = F, Cl, Br), the barrier energy is significantly reduced and the improvement of the catalytic efficiency of the superacid HA reaches 23.1 to 31.7%. In particular, for HMg 2 Br 5 , the barrier energy of the hydrogenation of ethene is only 36 kcal mol -1 , which shows that the reaction could proceed under experimental conditions. In addition, the results show that the catalytic efficiency of the superacid HA is related to the acidity of the superacid. In general, the greater the acidity, the lower the barrier energy and the easier the hydrogenation reaction. From the analysis of the bond order, the newly formed C-H bond of the transition state (TS3) in the concerted path, in which the H atom comes from the superacid catalyst, directly affects the barrier energy of the entire reaction. For the more acidic catalyst, this H atom is provided more easily, and then the formed C-H bond in the transition state is stronger. Consequently, this stronger bond leads to a more stable transition state, and hence to a lower energy barrier as well as a higher efficiency of the superacid catalyst. Therefore, a positive correlation between the acidity of the metal-free catalyst and its catalytic efficiency is expected in the hydrogenation reaction.